Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
  • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
  • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/102—Metallic powder coated with organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
  • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
  • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
  • B23K35/3006—Ag as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
  • B23K35/3013—Au as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J1/00—Adhesives based on inorganic constituents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
  • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
  • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
  • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
  • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
  • B22F1/054—Nanosized particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
  • B22F1/054—Nanosized particles
  • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting

Definitions

• the present invention relates to a bonding composition including inorganic particles and an organic component attached to at least a part of the surface of the inorganic particles.
• solders, conductive adhesives, silver pastes, anisotropic conductive films and the like have been used to mechanically and / or electrically and / or thermally bond metal parts and metal parts.
• the conductive adhesive, the silver paste, the anisotropic conductive film and the like may be used not only for metal parts but also for bonding ceramic parts and resin parts.
• bonding of a light emitting element such as an LED to a substrate, bonding of a semiconductor chip to a substrate, bonding of these substrates to a heat dissipation member, and the like can be mentioned.
• adhesives, pastes and films containing conductive fillers made of solder and metal are used for joining parts requiring electrical connection. Furthermore, since metals generally have high thermal conductivity, adhesives, pastes and films containing these solders and conductive fillers may be used to enhance heat dissipation.
• a light emitting element such as an LED
• a semiconductor device that operates at high temperature and high efficiency called power device is used to manufacture a semiconductor device.
• the calorific value tends to rise. Attempts have been made to improve the efficiency of devices and elements to reduce heat generation, but at present, sufficient results have not been achieved, and the working temperatures of devices and elements have been raised.
• a bonding material capable of securing sufficient bonding strength at a low bonding temperature for example, 300 ° C. or less
• the bonding material for bonding devices, elements, etc. is required to have heat resistance that can withstand sufficient rise in the working temperature due to the operation of the device after bonding and maintain sufficient bonding strength as the bonding temperature decreases.
• conventional bonding materials can not sufficiently cope. For example, solder joins members together through a process (reflow process) of heating a metal to the melting point or more, but since the melting point is generally specific to its composition, heating (joining) is attempted when the heat resistance temperature is increased. The temperature also rises.
• solder when several layers of elements and substrates are stacked and bonded using solder, it is necessary to go through the heating process by the number of layers to be stacked, and to prevent melting of the already bonded portion, solder used for the next bonding It is necessary to lower the melting point (bonding temperature) of the above, and the types of the solder composition are required as many as the number of layers to be superposed, and the handling becomes complicated.
• Patent Document 1 Japanese Patent Laid-Open No. 2008-63688 proposes fine particles which are used as main components of a bonding material to obtain higher bonding strength when bonding members to be bonded to each other. The problem of decomposition and deterioration of the resin component at the time of temperature rise is not solved.
• solder containing lead is conventionally used for high-temperature solder used at high service temperatures. Because lead is toxic, solder has a significant trend towards lead-free. Lead solder is still used because there is no other good alternative for high temperature solder, but from an environmental point of view there is a need for lead-free bonding materials.
• the object of the present invention is to obtain a high bonding strength by bonding at a relatively low temperature and no pressure, and to reduce the bonding strength due to the decomposition and deterioration of the resin component when the operating temperature rises. It is an object of the present invention to provide a bonding composition having heat resistance which is less likely to occur, in particular, a bonding composition containing metal particles.
• the present inventor contains inorganic metal particles and an organic component attached to at least a part of the surface of the inorganic metal particles.
• the optimization of the organic component is extremely effective in achieving the above object, and reaches the present invention.
• the present invention provides a bonding composition containing inorganic metal particles, and an organic component containing unsaturated hydrocarbon and an amine having 4 to 7 carbon atoms.
• the particle size of the inorganic metal particles constituting the bonding composition of the present invention is suitably a nanometer size, preferably 1 to 200 nm, so that melting point depression occurs, but if necessary, particles of micron meter size are added It is also possible. In this case, bonding is achieved by the melting point depression of nanometer sized particles around micron sized particles.
• organic components in the present invention are unsaturated hydrocarbons and carbon. Contains 4 to 7 amines.
• an amine having 4 to 7 carbon atoms is used as a so-called dispersant.
• a low-boiling amine having a relatively small number of carbon chains low-temperature calcinable inorganic metal particles can be obtained.
• the bonding composition of the present invention may contain other amines in addition to the amine having 4 to 7 carbon atoms.
• an amine having 4 to 7 carbon atoms can be optionally selected in the range of 0.001 to 30, but preferably 0.005 It is -20, more preferably 0.01-10.
• the unsaturated hydrocarbon among the organic components has a double bond, and the steric structure improves the dispersibility of the inorganic metal particles in the organic solvent and has the effect of suppressing aggregation of the inorganic metal particles. is there.
• the above-described amine contributes to the stability of the inorganic metal particles in a storage state, since the functional group is adsorbed on the surface of the inorganic metal particles with an appropriate strength to prevent mutual contact between the inorganic metal particles. Further, it is considered that, at the bonding temperature, the adhesion and bonding between the inorganic metal particles and the bonding between the inorganic metal particles and the base are promoted by moving and / or volatilizing from the surface of the inorganic metal particles.
• the unsaturated hydrocarbon preferably has a hydroxyl group.
• the hydroxyl group and the carboxyl group are easily coordinated to the surface of the inorganic metal particles, and the aggregation suppressing effect of the inorganic metal particles can be enhanced.
• the coexistence of the hydrophobic group and the hydrophilic group also has an effect of dramatically improving the wettability of the bonding composition and the bonding substrate.
• a functional group is not restricted to a hydroxyl group, A carboxyl group etc. may be sufficient.
• the unsaturated hydrocarbon is preferably ricinoleic acid. It is believed that ricinoleic acid has a carboxyl group and a hydroxyl group, and has the effect of adsorbing on the surface of the inorganic metal particles to disperse the inorganic metal particles uniformly and promoting the fusion of the inorganic metal particles.
• the volatilization of the organic matter requires heat and oxygen, as is the organic matter on the surface of the inorganic metal particles. It is considered that the inorganic metal particle sintering promoting effect of ricinoleic acid is because oxygen of carboxyl group and hydroxyl group promotes volatilization / decomposition of the organic substance adhering to the surface of the inorganic metal particle.
• Ricinoleic acid may be added as a dispersant for covering the surface of the inorganic metal particles at the time of synthesis of the inorganic metal particles, or may be added as an additive after purification of the inorganic metal particles.
• the composition molar ratio at the time of synthesis of the inorganic metal particles when the metal salt is 1, the unsaturated hydrocarbon can be arbitrarily selected in the range of 0.001 to 10, but preferably 0.005 to 5 And more preferably 0.01 to 3.
• the bonding composition of the present invention is applied to, for example, an alumina ceramic substrate coated with gold on the surface, the same substrate is placed from above, and the obtained laminate is heated at 300.degree.
• the temperature of the bonding composition is gradually raised by heating, the relatively volatile organic components are volatilized by the time the temperature reaches 200 ° C.
• the inorganic metal particles are not positively fused with each other yet, and the bonding composition in the applied state still has flexibility. There is. Therefore, even if the organic component turns into a gas and volatilizes to form a cavity-like portion (passage) after passing the gas, the bonding composition around it moves and fills the portion. Then, the connection of the fused inorganic metal particles is integrated, and sufficient bonding strength can be obtained, thereby improving the conductivity and the thermal conductivity.
• the amino group in one molecule of the amine having 4 to 7 carbon atoms has relatively high polarity and tends to cause interaction by hydrogen bonding, but these functional groups
• the moieties other than groups have relatively low polarity.
• amino groups tend to exhibit alkaline properties, respectively. Therefore, when the amine having 4 to 7 carbon atoms is localized (adhered) to at least a part of the surface of the inorganic metal particles in the bonding composition of the present invention (ie, at least one of the surfaces of the inorganic metal particles When the part is covered, the organic component and the inorganic metal particles can be made to have sufficient affinity to prevent aggregation of the inorganic metal particles.
• the organic component acts as a dispersant, so that the dispersion state of the inorganic metal particles in the dispersion medium is remarkably improved. That is, according to the bonding composition of the present invention, since the specific combination of organic substances is contained, the inorganic metal particles are less likely to aggregate, and the inorganic metal particles have good dispersibility even in the coating film, and they are uniformly fused. Strong bonding strength can be obtained.
• the bonding composition of the present invention is, in other words, a composition having colloidal particles composed of inorganic metal particles and an organic component as a main component, but is a colloidal dispersion further including a dispersion medium.
• the "dispersion medium” is to disperse the above-mentioned colloid particles in the dispersion liquid, a part of the constituent components of the above-mentioned colloid particles may be dissolved in the "dispersion medium".
• the term “main component” refers to the component with the highest content among the components.
• the inorganic metal particles be particles of at least one metal of gold, silver, copper, nickel, bismuth, tin or a platinum group element.
• the bonding composition of the present invention is preferably used for bonding metals.
• the inorganic metal particles and the organic component adhering to at least a part of the surface of the inorganic metal particles are contained, and by optimizing the organic components, the additive temperature can be reduced at a low bonding temperature. It is possible to provide a bonding composition capable of obtaining high bonding strength even under pressure.
• the bonding composition of the present embodiment is characterized by containing inorganic metal particles and an unsaturated hydrocarbon and an organic component containing an amine having 4 to 7 carbon atoms. Each of these components will be described below.
• the inorganic metal particles of the bonding composition of the present embodiment are not particularly limited, but the conductivity of the adhesive layer obtained using the bonding composition of the present embodiment It is preferable that the metal is a (precious) metal having a smaller ionization tendency than zinc, because the property can be improved.
• Such metals include, for example, at least one of gold, silver, copper, nickel, bismuth, tin, iron and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium and platinum).
• the metal is preferably particles of at least one metal selected from the group consisting of gold, silver, copper, nickel, bismuth, tin or a platinum group element, and it is more ionizable than copper or copper.
• Is preferably a small (precious) metal, that is, at least one of gold, platinum, silver and copper.
• These metals may be used alone or in combination of two or more, and as a method to be used in combination, when alloy particles containing a plurality of metals are used, or a metal having a core-shell structure or a multilayer structure Particles may be used.
• the conductivity of the adhesive layer formed using the bonding composition of the present embodiment is good, but in consideration of the problem of migration, Migration can be made less likely to occur by using a bonding composition consisting of silver and other metals.
• the "other metals” metals in which the above-mentioned ionization sequence is nobler than hydrogen, that is, gold, copper, platinum and palladium are preferable.
• the average particle diameter of the inorganic metal particles (or inorganic metal colloidal particles) in the bonding composition of the present embodiment is not particularly limited as long as the effects of the present invention are not impaired, but melting point depression occurs It is preferable to have such an average particle size, for example, 1 to 200 nm. More preferably, it is 2 to 100 nm. If the average particle size of the inorganic metal particles is 1 nm or more, a bonding composition capable of forming a good adhesive layer can be obtained, and the production of inorganic metal particles is practical without increasing the cost. Moreover, if it is 200 nm or less, the dispersibility of the inorganic metal particles hardly changes with time, which is preferable.
• inorganic metal particle of a micrometer size it is also possible to add and use the inorganic metal particle of a micrometer size together as needed.
• bonding can be performed by lowering the melting point of the nanometer-sized inorganic metal particles around the micrometer-sized inorganic metal particles.
• the particle size of the inorganic metal particle in the composition for joining of this embodiment is not necessarily constant.
• the bonding composition contains, as an optional component, a dispersion medium, a resin component, an organic solvent, a thickener, a surface tension regulator, etc. described later, it contains an inorganic metal colloidal particle component having an average particle diameter of more than 200 nm. In some cases, as long as the component does not cause aggregation and does not significantly impair the effect of the present invention, it may contain a particle component having an average particle diameter of more than 200 nm.
• the particle size of the inorganic metal particles in the bonding composition (metal colloid dispersion liquid) of the present embodiment can be measured by a dynamic light scattering method, a small angle X-ray scattering method, or a wide angle X-ray diffraction method.
• the crystallite diameter determined by the wide angle X-ray diffraction method is appropriate.
• measurement can be performed in a range of 2 ⁇ of 30 ° to 80 ° by the diffraction method using RINT-Ultima III manufactured by Rigaku Corporation.
• the sample may be measured by thinly spreading it so that the surface becomes flat on a glass plate having a depression of about 0.1 to 1 mm deep at the center.
• the crystallite diameter (D) calculated by substituting the half width of the obtained diffraction spectrum into the following Scheller equation using JADE manufactured by Rigaku Denki Co., Ltd. may be used as the particle diameter.
• D K ⁇ / Bcos ⁇
• K Scheller constant (0.9)
• ⁇ wavelength of X-ray
• B half width of diffraction line
• ⁇ Bragg angle.
• the organic component attached to at least part of the surface of the inorganic metal particle substantially constitutes inorganic metal colloid particles together with the above-mentioned inorganic metal particles as a so-called dispersant.
• the organic component trace organic substances contained as impurities in the metal from the beginning, trace organic substances mixed in the manufacturing process to be described later and attached to the metal components, residual reducing agents which could not be removed in the washing process, residual dispersants, etc.
• less than 1% by mass in the metal colloid particles is specifically intended as the above-mentioned "minor amount”.
• the organic component is an organic substance capable of covering inorganic metal particles to prevent aggregation of the inorganic metal particles and forming inorganic metal colloid particles, and the form of the coating is not particularly defined, but the present embodiment
• unsaturated hydrocarbon and an amine having 4 to 7 carbon atoms are included from the viewpoint of dispersibility and conductivity.
• these organic components are chemically or physically bonded to the inorganic metal particles, they are considered to be changed to anions or cations, and in the present embodiment, are derived from these organic components. Ions, complexes and the like are also included in the above organic components.
• the amine having 4 to 7 carbon atoms may be linear or branched as long as it has 4 to 7 carbon atoms, and may have a side chain.
• alkylamine such as butylamine, pentylamine, hexylamine, hexylamine (linear alkylamine, may have a side chain)
• cycloalkylamine such as cyclopentylamine, cyclohexylamine, allylamine such as aniline Etc.
• secondary amines such as dipropylamine, dibutylamine, piperidine and hexamethyleneimine
• tertiary amines such as tripropylamine, dimethylpropanediamine, cyclohexyldimethylamine, pyridine and quinoline.
• the above-mentioned amine having 4 to 7 carbon atoms may be, for example, a compound containing a functional group other than an amine, such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
• a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
• the number of carbons in the functional group is not included in the number of carbons of “amine having 4 to 7 carbons”.
• the number of nitrogen atoms derived from an amine is preferably equal to or more than the number of functional groups other than the amine.
• the above amines may be used alone or in combination of two or more.
• the boiling point at normal temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less.
• the bonding composition of this embodiment may contain a carboxylic acid in addition to the above-mentioned amine having 4 to 7 carbon atoms, as long as the effects of the present invention are not impaired.
• a carboxylic acid in addition to the above-mentioned amine having 4 to 7 carbon atoms, as long as the effects of the present invention are not impaired.
• the carboxyl group in one molecule of carboxylic acid has relatively high polarity and tends to cause interaction by hydrogen bonding, parts other than these functional groups have relatively low polarity. Furthermore, carboxyl groups tend to exhibit acidic properties.
• the carboxylic acid is localized (adhered) to at least a part of the surface of the inorganic metal particles in the bonding composition of the present embodiment (that is, when at least a part of the surface of the inorganic metal particles is coated)
• the organic component and the inorganic metal particles can be made to have a sufficient affinity, and the aggregation of the inorganic metal particles is prevented (the dispersibility is improved).
• carboxylic acid compounds having at least one carboxyl group can be widely used, and examples thereof include formic acid, oxalic acid, acetic acid, hexanoic acid, acrylic acid, octylic acid, oleic acid and the like.
• a part of carboxyl groups of the carboxylic acid may form a salt with the metal ion.
• 2 or more types of metal ions may be contained.
• the carboxylic acid may be, for example, a compound containing a functional group other than a carboxyl group, such as an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
• the number of carboxyl groups is preferably equal to or greater than the number of functional groups other than carboxyl groups.
• the carboxylic acids may be used alone or in combination of two or more.
• the boiling point at normal temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less.
• amines and carboxylic acids form amides.
• An amide group may be contained in the organic component because the amide group is also appropriately adsorbed on the surface of silver particles.
• the content of the organic component in the metal colloid in the bonding composition of the present embodiment is preferably 0.5 to 50% by mass. If the organic component content is 0.5% by mass or more, the storage stability of the resulting bonding composition tends to be improved, and if it is 50% by mass or less, the conductivity of the bonding composition tends to be good. There is. A more preferable content of the organic component is 1 to 30% by mass, and a further preferable content is 2 to 15% by mass.
• composition ratio (mass) in the case of using an amine and a carboxylic acid in combination can be optionally selected in the range of 1/99 to 99/1, but is preferably 20/80 to 98/2, and further, Preferably, it is 30/70 to 97/3.
• amine or carboxylic acid plural kinds of amines or carboxylic acids may be used.
• Examples of the unsaturated hydrocarbon contained in the bonding composition of the present embodiment include ethylene, acetylene, benzene, acetone, 1-hexene, 1-octene, 4-vinylcyclohexene, cyclohexanone, terpene alcohol, allyl alcohol, Oleyl alcohol, 2-palmitoleic acid, petroselinic acid, oleic acid, oleidic acid, ericic acid, thianicic acid, ricinoleic acid, linoleic acid, linoleic acid, linolenic acid, linolenic acid, arachidonic acid, acrylic acid, methacrylic acid, gallic acid and salicylic acid etc. .
• unsaturated hydrocarbons having a hydroxyl group are preferable.
• the hydroxyl group is easily coordinated to the surface of the inorganic metal particle, and aggregation of the inorganic metal particle can be suppressed.
• the unsaturated hydrocarbon having a hydroxyl group include terpene alcohols, allyl alcohol, oleyl alcohol, thianic acid, ricinoleic acid, gallic acid and salicylic acid.
• they are unsaturated fatty acids having a hydroxyl group, and examples thereof include thianic acid, ricinoleic acid, gallic acid and salicylic acid.
• the unsaturated hydrocarbon is preferably ricinoleic acid.
• Ricinoleic acid has a carboxyl group and a hydroxyl group, and is adsorbed on the surface of the inorganic metal particles to uniformly disperse the inorganic metal particles, and promotes fusion of the inorganic metal particles.
• the bonding composition of the present embodiment is provided with functions such as appropriate viscosity, adhesion, drying property, or printability according to the purpose of use, as long as the effects of the present invention are not impaired.
• Dispersion medium for example, an oligomer component serving as a binder, a resin component, an organic solvent (which may dissolve or disperse part of the solid content), a surfactant, a thickener, or surface tension. You may add arbitrary components, such as a modifier. Such optional components are not particularly limited.
• various media can be used as long as the effects of the present invention are not impaired, and examples thereof include hydrocarbons and alcohols.
• hydrocarbon examples include aliphatic hydrocarbons, cyclic hydrocarbons, alicyclic hydrocarbons and the like, which may be used alone or in combination of two or more.
• aliphatic hydrocarbons include saturated or unsaturated aliphatic hydrocarbons such as tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methylpentane, normal paraffin, isoparaffin, etc. Can be mentioned.
• cyclic hydrocarbons examples include toluene and xylene.
• alicyclic hydrocarbon for example, limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, sinene, orange flavor, terpinolene, terpinolene (also referred to as terpinolene), ferandrene, mentadiene, tereben,
• Examples thereof include dihydrocymene, mosulene, isoterpinene, isoterpinene (also referred to as isoterpinene), clitomene, kaoutushin, kajepsin, eulimen, pinene, turpent, mentane, pinan, terpene, cyclohexane and the like.
• the alcohol is a compound containing one or more OH groups in the molecular structure, and includes aliphatic alcohols, cyclic alcohols and alicyclic alcohols, which may be used alone or in combination of two or more. It is also good. In addition, a part of the OH group may be derived to an acetoxy group or the like within the range not impairing the effects of the present invention.
• aliphatic alcohols examples include heptanol, octanol (1-octanol, 2-octanol, 3-octanol etc.), decanol (1-decanol etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-one Examples thereof include saturated or unsaturated C 6-30 aliphatic alcohols such as hexanol, octadecyl alcohol, hexadecenol and oleyl alcohol.
• cyclic alcohols examples include cresol and eugenol.
• alicyclic alcohol for example, cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers, or any mixture thereof), terpene alcohol such as dihydroterpineol (monoterpene alcohol, etc.) And dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perylyl alcohol, pinocarbeol, sobrerol, verbenol and the like.
• cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers, or any mixture thereof)
• terpene alcohol such as dihydroterpineol (monoterpene alcohol, etc.)
• dihydroterpineol myrtenol, sobrerol, menthol, carveol, perylyl alcohol, pinocarbeol, sobrerol, verbenol
• the content in the case of including the dispersion medium in the composition for bonding of the present embodiment may be adjusted according to desired characteristics such as viscosity, and the content of the dispersion medium in the composition for bonding is 1 to 30 mass. % Is preferred. When the content of the dispersion medium is 1 to 30% by mass, the effect of adjusting the viscosity can be obtained in the range which is easy to use as the bonding composition. A more preferable content of the dispersion medium is 1 to 20% by mass, and a further preferable content is 1 to 15% by mass.
• the resin component examples include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, terpene resins, and the like. These may be used alone or in combination of two or more.
• organic solvent except for those mentioned above as the dispersion medium, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, 1,3-propanediol, 1,2-propanediol, 1 2,4-butanediol, 1,2,6-hexanetriol, 1-ethoxy-2-propanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, weight average molecular weight in the range of 200 to 1,000 Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol having a weight average molecular weight of 300 or more and 1,000 or less, N, N-dimethylformamide, dimethyl sulfoxide, N Methyl-2-pyrrolidone, N, N- dimethylacetamide, glycerin, or acetone and the like may be used each of which alone or in combination of two or more.
• clay minerals such as clay, bentonite or hectorite
• polyester emulsion resin acrylic emulsion resin, polyurethane emulsion resin or emulsion such as blocked isocyanate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose And cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methylcellulose; polysaccharides such as xanthan gum and guar gum; and the like.
• acrylic emulsion resin acrylic emulsion resin
• polyurethane emulsion resin or emulsion such as blocked isocyanate
• methyl cellulose carboxymethyl cellulose
• hydroxyethyl cellulose And cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methylcellulose
• polysaccharides such as xanthan gum and guar gum; and the like.
• the surfactant that can be used in the present embodiment is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used.
• an anionic surfactant for example, an alkyl benzene sulfonate can be used.
• quaternary ammonium salts Fluorine-based surfactants are preferred because the effect can be obtained with a small addition amount.
• the method of adjusting the amount of organic components in a predetermined range is mentioned later, it is simple to heat and adjust. Moreover, you may carry out by adjusting the quantity of the organic component added at the time of producing inorganic metal particle, and may change the washing
• the heating can be performed in an oven, an evaporator, or the like, and may be performed under reduced pressure. When carried out under normal pressure, it can be carried out in the atmosphere or in an inert atmosphere. Furthermore, the above-mentioned amines (and carboxylic acids) can be added later to finely adjust the amount of organic components.
• the bonding composition of the present embodiment includes, as a main component, inorganic metal colloid particles obtained by colloiding inorganic metal particles described later, and regarding the form of such inorganic metal colloid particles, for example, the surface of inorganic metal particles Inorganic metal colloidal particles in which an organic component adheres to a part of the inorganic metal colloid particles, inorganic metal colloidal particles in which the surface is covered with an organic component with the inorganic metal particles as a core, and these are mixed Although the inorganic metal colloid particle etc. which are comprised are mentioned, it does not specifically limit. Among them, inorganic metal colloidal particles having an inorganic metal particle as a core and having a surface coated with an organic component are preferable. Those skilled in the art can appropriately prepare inorganic metal colloidal particles having the above-mentioned form, using techniques well known in the art.
• the bonding composition of the present embodiment is a fluid mainly composed of colloidal particles composed of inorganic metal particles and an organic component, and in addition to the inorganic metal particles and the organic components constituting the inorganic metal colloidal particles, You may contain the organic component which does not comprise inorganic metal colloid particle
• the viscosity of the composition for bonding of the present embodiment may be suitably adjusted within the range that does not impair the effect of the present invention, but it may be, for example, in the viscosity range of 0.01 to 5000 Pa ⁇ S.
• a viscosity range of 1 to 1000 Pa ⁇ S is more preferable, and a viscosity range of 1 to 100 Pa ⁇ S is particularly preferable.
• a wide method can be applied as a method of apply
• a method for applying the bonding composition onto the substrate for example, dipping, screen printing, spray method, bar coating method, spin coating method, spin coating method, ink jet method, dispenser method, pin transfer method, brush coating method, casting method It becomes possible to adopt it by appropriately selecting from among a method, a flexo method, a gravure method, an offset method, a transfer method, a hydrophilic / hydrophobic pattern method, a syringe method and the like.
• the viscosity may be adjusted by adjusting the particle size of the inorganic metal particles, adjusting the content of the organic substance, adjusting the addition amount of the dispersion medium and other components, adjusting the compounding ratio of each component, adding a thickener, etc. it can.
• the viscosity of the bonding composition can be measured, for example, by a cone and plate viscometer (for example, a rheometer MCR301 manufactured by Anton Paar).
• adjustment of the amount of organic components and the weight reduction rate is not particularly limited, but it is convenient to perform adjustment by heating. Moreover, you may carry out by adjusting the quantity of the organic component added at the time of producing inorganic metal particle, and may change the washing
• Heating can be performed in an oven, an evaporator or the like.
• the heating temperature may be in the range of about 50 to 300 ° C., and the heating time may be in the range of several minutes to several hours.
• the heating may be performed under reduced pressure. By heating under reduced pressure, the amount of organic substance can be adjusted at a lower temperature. When carried out under normal pressure, it can be carried out in the atmosphere or in an inert atmosphere.
• amines and carboxylic acids can also be added later to fine-tune the organic fraction.
• the method of preparing the inorganic metal particles coated with the organic component of the present embodiment is not particularly limited, but, for example, a method of preparing a dispersion containing inorganic metal particles and then washing the dispersion, etc. It can be mentioned.
• a step of preparing a dispersion containing inorganic metal particles for example, metal salts (or metal ions) dissolved in a solvent may be reduced as described below, and as a reduction procedure, a chemical reduction method may be used. You can adopt the procedure based on
• the inorganic metal particles coated with the organic component as described above are a metal salt of the metal constituting the inorganic metal particles, an organic substance as a dispersant, and a solvent (basically an organic type such as toluene, It may be prepared by reducing a raw material liquid (which may contain water) (a part of the components may be dispersed without being dissolved).
• inorganic metal colloid particles in which an organic component as a dispersant is attached to at least a part of the surface of the inorganic metal particles are obtained.
• this inorganic metal colloidal particle can be provided as the bonding composition of the present embodiment by itself, it can be added from the inorganic metal colloidal dispersion by adding it to the dispersion medium in the process described later, if necessary. It can also be obtained as a bonding composition.
• various known metal salts or hydrates thereof can be used.
• the method of reducing these metal salts in the raw material solution is not particularly limited, and examples thereof include a method of using a reducing agent, a method of irradiating light such as ultraviolet light, an electron beam, ultrasonic waves or thermal energy. Among them, a method using a reducing agent is preferable from the viewpoint of easy operation.
• the reducing agent examples include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone and hydrazine; hydrogen compounds such as sodium borohydride, hydrogen iodide, hydrogen gas and the like; And oxides such as sulfite; for example, ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate, tin oxide, sulfuric acid Low valent metal salts such as tin; for example, sugars such as ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D-glucose etc. There is no particular limitation as long as it can be reduced. When the above reducing agent is used, light and / or heat may
• organic component, solvent and reducing agent for example, the above metal salt is dissolved in an organic solvent (for example, toluene etc.) to be a metal salt
• an organic solvent for example, toluene etc.
• a solution is prepared, an organic substance as a dispersant is added to the metal salt solution, and then a solution in which a reducing agent is dissolved is gradually dropped there.
• the organic metal-coated inorganic metal particles can be reliably obtained by washing the solution containing the inorganic metal particles to remove excess residue.
• a dispersion liquid containing inorganic metal particles coated with an organic component is allowed to stand for a certain period of time, the resulting supernatant liquid is removed, alcohol (such as methanol) is added, and stirring is performed again.
• alcohol such as methanol
• the method of repeating the process of removing the supernatant liquid that has been left to stand for a certain period of time is repeated several times, the method of performing centrifugation instead of the above-mentioned standing, the method of desalting by an ultrafiltration device or ion exchange device It can be mentioned.
• the inorganic metal colloid dispersion liquid is obtained by mixing the inorganic metal particles coated with the organic component obtained above and the dispersion medium described in the present embodiment.
• the method of mixing the inorganic metal particles coated with the organic component and the dispersion medium is not particularly limited, and the method can be carried out by a conventionally known method using a stirrer, a stirrer or the like. It may be stirred with a spatula or the like and an ultrasonic homogenizer of appropriate output may be applied.
• the production method thereof is not particularly limited.
• a dispersion containing inorganic metal particles and a dispersion containing other inorganic metal particles may be separately prepared and then mixed, a silver ion solution and other metal ions. The solution may be mixed and then reduced.
• the present inventor uses the bonding composition of the present embodiment described above as the bonding composition in the bonding composition applying step, the first bonding member and the second bonding member. It has been found that it is possible to more reliably join (to obtain a joined body) with a high bonding strength.
• “application” of the bonding composition of the present embodiment is a concept including the case of applying the bonding composition in a planar manner and the case of applying (drawing) in a linear manner.
• the shape of the coating film made of the bonding composition in the state of being applied and before firing by heating can be made into a desired shape. Therefore, in the bonded body of the present embodiment after firing by heating, the bonding composition is a concept including both planar bonding layers and linear bonding layers, and these planar bonding layers and linear bonding layers
• the bonding layer may be continuous or discontinuous, and may include continuous portions and discontinuous portions.
• the first bonding member and the second bonding member that can be used in the present embodiment may be anything that can be applied by applying a bonding composition, firing by heating, and bonding, and in particular Although it is not, it is preferable that the member is heat resistant enough not to be damaged by the temperature at the time of bonding.
• a material which constitutes such a member to be joined for example, polyamide (PA), polyimide (PI), polyamide imide (PAI), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) And polyester, polycarbonate (PC), polyether sulfone (PES), vinyl resin, fluorine resin, liquid crystal polymer, ceramics, glass, metal or the like.
• a metal-made joining member is preferable.
• the metal bonded member is preferable because it is excellent in heat resistance and excellent in affinity to the bonding composition of the present invention in which the inorganic particles are metal.
• the members to be joined may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible.
• the thickness of the substrate can also be selected as appropriate.
• a member having a surface layer or a member subjected to surface treatment such as hydrophilization treatment may be used to improve adhesion or adhesion or for other purposes.
• various methods can be used, but as described above, for example, dipping, screen printing, spray type, bar coat type, spin coat type, inkjet It can be used by appropriately selecting from among a formula, a dispenser type, a pin transfer method, a coating type by brush, a casting type, a flexo type, a gravure type, a syringe type and the like.
• the coated film after the application as described above is fired by heating to a temperature of, for example, 300 ° C. or less, in a range not damaging the members to be joined, to obtain the bonded body of the present embodiment.
• a bonding layer having excellent adhesion to a member to be bonded can be obtained, and strong bonding strength can be more reliably obtained. can get.
• the binder component when the bonding composition contains a binder component, the binder component is also sintered from the viewpoint of improving the strength of the bonding layer and the bonding strength between members to be bonded.
• the main purpose of the binder component may be to control firing conditions to remove all the binder component.
• the method of performing the baking is not particularly limited, and for example, the temperature of the bonding composition applied or drawn on the member to be bonded is, for example, 300 ° C. or less using a conventionally known oven or the like. It can join by baking.
• the lower limit of the firing temperature is not necessarily limited, and is preferably a temperature at which the members to be joined can be joined, and a temperature within the range that does not impair the effects of the present invention.
• the bonding composition after the above baking it is preferable that the remaining amount of the organic substance be as small as possible in that the bonding strength is as high as possible, but a part of the organic substance remains as long as the effect of the present invention is not impaired. It does not matter.
• the bonding composition of the present invention contains an organic substance, it does not obtain the bonding strength after firing by the action of an organic substance unlike the conventional one using thermosetting such as epoxy resin, for example. As described above, sufficient bonding strength can be obtained by fusing the fused inorganic metal particles. For this reason, there is no possibility that the bonding strength will be reduced even if the remaining organic matter is left in a working environment higher than the bonding temperature after bonding and the remaining organic matter is degraded or decomposed / disappeared, and therefore the heat resistance is excellent. There is.
• bonding composition of the present embodiment for example, bonding with a bonding layer that exhibits high conductivity even with baking at a low temperature of about 150 to 200 ° C. can be realized.
• the members can be joined together.
• the firing time is not particularly limited, and may be a firing time that can be joined depending on the firing temperature.
• surface treatment of the bonding member may be performed.
• the surface treatment method include a method of performing dry treatment such as corona treatment, plasma treatment, UV treatment, and electron beam treatment, and a method of providing a primer layer and a conductive paste-receptive layer in advance on a substrate.
• the present invention is not limited to these.
• the inorganic metal colloid dispersion liquid employing metal particles as the inorganic particles has been described, but, for example, tin-doped indium oxide excellent in conductivity, thermal conductivity, dielectricity, ion conductivity, etc., alumina Inorganic particles such as barium titanate and lithium iron phosphate can also be used.
• Example 1 To 300 mL of toluene (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), 50 g of hexylamine (EP grade, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was thoroughly stirred with a magnetic stirrer. While stirring, 10 g of silver nitrate (special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 10 g of oleic acid (first grade made by Wako Pure Chemical Industries, Ltd.) and hexanoic acid (Wako Pure Chemical Industries ( A special solution of 5 g) was added successively to prepare a toluene solution of silver nitrate.
• toluene special grade, manufactured by Wako Pure Chemical Industries, Ltd.
• this solution prepared by adding 2 g of sodium borohydride (for Wako Pure Chemical Industries, Ltd. Chemical) to 100 mL of ion-exchanged water to this toluene solution of silver nitrate mL of sodium borohydride aqueous solution was added dropwise and stirring was continued for 1 hour to form silver particles. Thereafter, 500 mL of methanol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added to precipitate silver particles. Furthermore, after completely settling silver particles by centrifugation, the reaction residue, the solvent, and the like contained in the supernatant were removed.
• sodium borohydride for Wako Pure Chemical Industries, Ltd. Chemical
• the precipitate (silver particle composition) containing silver particles remaining after removing the supernatant was decompressed for a few minutes using a diaphragm pump to well evaporate a small amount of remaining methanol, and The silver particle composition 1 was obtained by heating in an oven at 20 ° C. for 20 minutes to reduce the amount of organic matter including hexylamine, oleic acid and hexanoic acid to an appropriate amount.
• the obtained laminated body was put into the hot air circulation type oven adjusted to 200 degreeC, and the baking process by the heating for 120 minutes was performed in air
• a bonding strength test (share height: 10 microns from the substrate, shear tool speed: 0.01 mm / sec) is performed using a bond tester (PTR-1101 manufactured by Lesca) at normal temperature
• the bonding strength at peeling was converted to the bottom area of the chip.
• the numerical values in the evaluation results are in MPa.
• Example 2 A bonding composition 2 was prepared in the same manner as in Example 1 except that ricinoleic acid was not added, and bonding strength was measured. The results are shown in Table 1.
• Example 3 A bonding composition 3 was prepared in the same manner as in Example 1 except that ricinoleic acid was used instead of oleic acid, and the bonding strength was measured. The results are shown in Table 1.
• Example 4 A bonding composition 4 was prepared in the same manner as in Example 1 except that ricinoleic acid was not further added to the silver particle composition obtained using ricinoleic acid instead of oleic acid, and the bonding strength was measured. . The results are shown in Table 1.
• Comparative bonding composition 1 was prepared in the same manner as in Example 1 except that oleic acid and ricinoleic acid were not added, and bonding strength was measured. The results are shown in Table 1.
• Comparative bonding composition 2 was prepared in the same manner as in Example 1 except that dodecylamine was used instead of hexylamine, and then ricinoleic acid was not added, and bonding strength was measured. The results are shown in Table 1.
• Comparative bonding composition 3 was prepared and bonding strength was measured in the same manner as in Example 1 except that oleylamine was used instead of hexylamine, and then ricinoleic acid was not added. The results are shown in Table 1.

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